KR101132049B1 - Aqueous coating agent for electronic component - Google Patents

Abstract

A coating agent for electronic components, comprising a polymer (1) comprising a repeating unit derived from (A) a fluorine-containing acrylate monomer and a repeating unit derived from (B) an amino group-containing monomer, and an aqueous liquid medium (2) Is disclosed. A coating is easily formed on the surface of an electronic component, and furthermore, a coating agent capable of forming a coating film having excellent chemical resistance, electrical insulation, weather resistance, and durability as well as moisture resistance is provided.

Description

Aqueous Coating for Electronic Components {AQUEOUS COATING AGENT FOR ELECTRONIC COMPONENT}

The present invention relates to an aqueous coating agent that imparts excellent moisture resistance, water and oil repellency, and antifouling property to electronic parts and electric parts. In the present invention, the term "electronic component" means both an electronic component and an electrical component.

Control of outdoor electronic and electrical equipment (e.g. telephones, signals, air conditioners, outdoor units, switchboards, columnar capacitors, mobile phones, mobile relay antennas, automotive electronics, boat electronics, vending machines, mobile personal computers, etc.) For this purpose, the provision of electronic and electrical circuit boards is progressing. Thereby, metal wiring may be corroded by acid, salt, etc. by rain, moisture, dust, insects, etc., and a circuit may be destroyed, and it becomes a problem. Therefore, in recent years, after mounting an electronic and electrical component, it is generally performed to coat a circuit board surface and to improve moisture resistance.

In order to form a moisture proof coating, the method of apply | coating a water / oil repellent agent is known.

The method of applying the water / oil repellent agent is to dissolve a low molecular weight silicone-based or fluorine-based compound (perfluoropolyether oligomer, etc.) having poor film-forming ability in a solvent and spray coating the circuit board (Patent Document 1 (Japanese Patent No. 3122443)), therefore, no coating is formed on the surface of the circuit board, and the effect is also reduced over time.

Patent document 2 (Japanese Unexamined-Japanese-Patent No. 61-189693) discloses apply | coating the coating component in which the polyfluoroalkyl group containing polymer is melt | dissolved in the incombustible low boiling point organic solvent to an electronic component. However, the organic solvent has a problem in terms of the coating operation and the environment.

Next, environmental problems of the PFOA will be described. Long-chain fluorocarbons from recent studies [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf). Environmental concerns about perfluorooctanoic acid (PFOA), a type of roalkyl compound, have been clarified, and on April 14, 2003, the US Environmental Protection Agency (EPA) conducted a scientific investigation of PFOA. Announced that it will strengthen.

Meanwhile, the Federal Register (FR Vol. 68, No. 73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) or EPA Environmental News FOR RELEASE MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) or EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) declares that telomers are likely to produce PFOA by degradation or metabolism (telomer means long-chain fluoroalkyl groups). It also discloses that telomers are used in many products, such as antifoaming agents, care products, cleaning products, carpets, textiles, paper, leather, etc., which have water and oil repellency and antifouling properties.

In the case where the Rf group carbon number of the fluorine-containing copolymer conventionally mentioned is 8 or more, it is problematic to include PFOA and PFOA-like substances having bioaccumulation properties, and the short-chain Rf group-containing fluoroacrylates having 6 or less carbon atoms are quickly used. There is a need for a fluorine-containing polymer with improved affinity to polymers and affinity with other materials and skin.

Japanese Patent No. 332443 Japanese Patent Laid-Open No. 61-189693

An object of the present invention is to provide a moisture proof coating (that is, an aqueous coating composition) excellent in coating workability and environmental properties (without using an organic solvent).

Another object of the present invention is to provide a moisture-proof coating that can be easily formed on the surface of an electronic component and can form a coating film having excellent chemical resistance, electrical insulation, weather resistance, and durability as well as moisture resistance.

That is, this invention relates to the moisture proof coating agent for electronic components containing a fluorine-containing compound (1) and an aqueous liquid medium (2).

The fluorine-containing compound (1) is generally a fluorine-containing polymer. Fluorine-containing compound (1),

(A) It is preferable that it is a polymer containing the repeating unit derived from the fluorine-containing acrylate monomer. Fluorine-containing compound (1),

(A) repeating units derived from fluorine-containing acrylate monomers, and

(B) repeating units derived from amino group-containing monomers

It is especially preferable that it is a polymer containing.

In the present invention, the fluorine-containing polymer has sufficient solubility in required water. Higher solubility is obtained when it has a C7 or less, especially 6 or less short-chain fluoroalkyl group. The fluorine-containing polymer of the present invention has sufficiently high water solubility and imparts high moisture resistance on the substrate.

The coating agent of this invention can be dried in low temperature and a short time, and can form a film easily on the surface of an electronic component. The film has excellent moisture resistance, water and oil repellency and antifouling property, and is excellent in the persistence of these properties. The film formed from the coating agent of the present invention has high moisture resistance, water and oil repellency and antifouling property even if the film thickness is thin. In addition, the coating is excellent in chemical resistance, electrical insulation, weather resistance and durability.

In the present invention, the "acrylate monomer" includes not only an acrylate in which the α position is a hydrogen atom, but also an acrylate in which a hydrogen atom in the α position is substituted with a substituent such as a methyl group or a halogen atom.

In the fluorine-containing polymer, examples of the fluorine-containing acrylate monomer (A) include at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group, and a fluoroether group (hereinafter referred to as "fluorine-containing group"). ), And

[Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are hydrogen atoms) , A fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, and the like. It is a monomer which has an unsaturated group.

The acrylate monomer which has a fluorine-containing group is represented by following General formula (I), for example.

<Formula I>

Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are hydrogen atoms, Fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group,

Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic aliphatic group, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or -CH ₂ CH (OY ¹ ) CH ₂ -group (wherein Y ¹ is a hydrogen atom or an acetyl group),

Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit -C ₃ F ₆ O-, -C ₂ F ₄ O-, and -CF ₂ O- It is a fluoroether group whose total number of at least 1 sort (s) of repeating units chosen from the group which consists of 1-200 is 1-200.

In the general formula (I), when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group. Specific examples of the Rf group are those having 1 to 7 carbon atoms, for example

등을 들 수 있다. Rf기가 플루오로알킬기인 경우에, 상술한 PFOA의 관점 및 기능의 관점에서, Rf기의 탄소수는 1 내지 7, 예를 들어 2 내지 6, 특히 4 내지 6, 특별히 6인 것이 바람직하다.

And the like. In the case where the Rf group is a fluoroalkyl group, it is preferable that the carbon number of the Rf group is 1 to 7, for example, 2 to 6, especially 4 to 6, especially 6, from the viewpoint of the above-described PFOA and function.

When the Rf group is a fluoroalkenyl group, examples of the Rf group include -CF = CF (CF ₃ ), -CF = C (CF ₃ ) ₂ , -CF = C (CF ₃ ) (CF ₂ CF ₂ CF ₃ ),- CF = C (CF ₃ ) (CF (CF ₃ ) ₂ ), -C (CF ₃ ) = CF (CF (CF ₃ ) ₂ ),-C (CF ₂ CF ₃ ) = C (CF ₃ ) _2, etc. . In the case where the Rf group is a fluoroalkenyl group, it is preferable that the carbon number of the Rf group is 2 to 7, especially 3 to 6, especially 6.

), 아민기(예를 들어, H₂N-), 카르복실산기(예를 들어, HOOC-), 산 할라이드기(예를 들어, F(O=)C-), 클로로메틸기(ClH₂C-)이다. 플루오로에테르기는 옥시퍼플루오로알킬렌 반복 단위 및 말단기에 추가하여, 탄소수 1 내지 10의 플루오로알킬렌기, 특히 퍼플루오로알킬렌기를 가져도 된다. 탄소수 1 내지 10의 플루오로알킬렌기의 예는 -CF₂- 및 -CF₂CF₂-이다.When the Rf group is a fluoroether group, the fluoroether group is at least one repeating unit selected from the group consisting of -C ₃ F ₆ O-, -C ₂ F ₄ O-, and -CF ₂ O- (oxyperfluoroalkyl Leng). -C ₃ F ₆ O- is -CF ₂ CF ₂ CF ₂ O- or -CF ₂ C (CF ₃ ) FO-. -C ₂ F ₄ O- is generally -CF ₂ CF ₂ O-. The total number of oxyperfluoroalkylene repeat units is 1 to 200, for example 1 to 100, in particular 5 to 50. The fluoroether group has a terminal group which directly bonds to an oxyperfluoroalkylene repeating unit. Examples of terminal groups include hydrogen atoms, halogen atoms (e.g., fluorine atoms), alcohol groups (e.g., HOCH _2- ), epoxy groups (e.g.,

), An amine group (eg H ₂ N-), carboxylic acid group (eg HOOC-), acid halide group (eg F (O =) C-), chloromethyl group (ClH ₂ C) -)to be. The fluoroether group may have a fluoroalkylene group having 1 to 10 carbon atoms, in particular a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating units and terminal groups. Examples of fluoroalkylene groups having 1 to 10 carbon atoms are -CF ₂ -and -CF ₂ CF _2- .

Examples of the fluoroether group (particularly perfluoroether group) as an example of the Rf group are as follows.

Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic aliphatic group, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or -CH ₂ CH (OY ¹ ) CH ₂ -group (wherein Y ¹ is a hydrogen atom or an acetyl group). The aliphatic group is preferably an alkylene group (especially having 1 to 4 carbon atoms, for example 1 or 2). The aromatic group and the cyclic aliphatic group may or may not be substituted.

Examples of the fluorine-containing acrylate monomers are as follows.

In the formula, Rf is preferably a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit -C ₃ F ₆ O-, -C ₂ F ₄ O- And a fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of -CF ₂ O-.

An amino group containing monomer (B) is a compound which has an amino group and a carbon-carbon double bond. It is preferable that an amino group containing monomer (B) does not contain a fluorine atom.

Examples of the amino group-containing monomer (B) are those represented by the following general formula (II).

<Formula II>

Wherein R ¹¹ , R ¹² , R ²¹ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y ¹¹ is an oxygen atom or NH, and Z is a branched or straight chain having 1 to 10 carbon atoms It is an alkylene group, and R <^11> and R <^12> may combine with each other, and may form the ring with the adjacent nitrogen atom.

Since a copolymer contains an amino group, when a salt is formed by protonic acid, for example, when dissolves in water, it dissociates and shows cationicity.

R ¹¹ , R ¹² and R ²¹ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, and the like). R ²¹ is preferably a hydrogen atom or a methyl group. When R ¹¹ and R ¹² form a ring together with the nitrogen atom adjacent to bond to one another, also to the R ¹¹ and R ¹² bonded through a hetero atom such as nitrogen atom, oxygen atom, sulfur atom. As a ring which R <^11> and R <^12> combine with each other and form with the adjacent nitrogen atom, an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. are mentioned, for example.

As an alkylene group which is Z, a linear or branched C1-C6 (preferably C1-C4) alkylene group, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group, is mentioned.

Specific examples of the amino group-containing monomer (B) include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylamino Compounds in which Y ¹¹ is an oxygen atom in the formula (II) such as propyl (meth) acrylate and diethylaminopropyl (meth) acrylate; The compound etc. which Y <^11> is NH in Formula (II), such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide, are mentioned. An amino group containing monomer (B) can be used individually or in combination of 2 or more types.

The monomer which comprises a fluoropolymer may contain a hydrophilic non-fluorine monomer (C) in addition to monomer (A) and (B). Hydrophilic non-fluorine monomer (C) has hydrophilicity and does not contain a fluorine atom.

Examples of hydrophilic groups are oxyalkylene groups.

The hydrophilic non-fluorine monomer (C) may be a monomer having an oxyalkylene group (hydrocarbon group having 2 to 6 carbon atoms of the alkylene group) and a carbon-carbon double bond.

Hydrophilic groups that are oxyalkylene groups are nonionic. The number of oxyalkylene groups in the hydrophilic non-fluorine monomer (C) may be 2 to 200, for example, 3 to 50.

The hydrophilic non-fluorine monomer (C) may be polyalkylene glycol mono (meth) acrylate and / or polyalkylene glycol di (meth) acrylate.

The molecular weight of the hydrophilic non-fluorine monomer (C) may be 100 or more, for example 150 or more, in particular 200 or more, in particular 250 to 3000.

It is preferable that polyalkylene glycol mono (meth) acrylate is represented by following General formula (III). n may especially be 3-30, for example, 4-20.

<Formula III>

Wherein,

X ¹ is a hydrogen atom or a methyl group,

X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms,

R is an alkylene group having 2 to 6 carbon atoms,

n is an integer from 2 to 90.

R in formula III is preferably ethylene, propylene and butylene, especially ethylene groups.

R in Formula (III) may be a combination of two or more kinds of alkylene groups. In that case, at least one of R is preferably an ethylene group. As a combination of R, the combination of an ethylene group / a propylene group, and the combination of an ethylene group / butylene group are mentioned.

The hydrophilic non-fluorine monomer (C) may be a mixture of two or more kinds. In that case, it is preferable that at least one of the hydrophilic non-fluorine monomers (C) is R in the general formula (III) being an ethylene group.

Although the following can be illustrated, the specific example of a hydrophilic non-fluorine monomer (C) is not limited to these, for example.

The monomer which comprises a fluoropolymer may contain another monomer (D) as needed in addition to monomer (A), (B), (C). It is preferable that another monomer (D) is a non-fluorine monomer. Examples of other monomers (D) include hydrocarbon group-containing monomers, ethylene, vinyl acetate, vinyl halides (for example, vinyl chloride), vinylidene halides (for example, vinylidene chloride), acrylonitrile, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate Although vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, butadiene, etc. are illustrated, it is not limited to these.

As another example of another monomer (D), the monomer which has a silane group is mentioned. It is preferable that the monomer which has a silane group is a compound which has a silane group (especially a terminal silane group) and a carbon-carbon double bond. The monomer which has a silane group may be a terminal silane coupling agent or the monomer which has a silane coupling agent in a side chain.

The specific example of the monomer which has a silane group is as follows.

The weight average molecular weight of the fluorine-containing polymer may be, for example, 1000 to 1000000, especially 2000 to 100000, and particularly 4000 to 20000. The weight average molecular weight of a fluoropolymer is calculated | required by GPC (gel permeation chromatography) (polystyrene conversion).

The fluorine-containing polymer is dissolved in water. The solubility of the fluorine-containing polymer (the amount of the fluorine-containing polymer that can be dissolved with respect to 100 g of water at 25 ° C) may be 5 g or more, for example, 10 g or more, particularly 20 g or more. The upper limit of the solubility may be 500 g, for example 200 g.

The fluorine-containing polymer may be composed of a combination of repeating units derived from the following monomers.

(1) Monomer (A) + Monomer (B)

(2) Monomer (A) + Monomer (B) + Monomer (C)

(3) Monomer (A) + Monomer (B) + Monomer (D)

(4) Monomer (A) + Monomer (B) + Monomer (C) + Monomer (D)

In the fluorine-containing polymer, based on 100 parts by weight of the monomer (A),

The amount of monomer (B) is 1 to 500 parts by weight, for example 2 to 100 parts by weight, in particular 3 to 80 parts by weight, in particular 5 to 70 parts by weight,

The amount of monomer (C) is 0 to 10 parts by weight, for example 1 to 5 parts by weight,

The amount of the monomer (D) may be 0 to 10 parts by weight, for example 1 to 5 parts by weight.

The fluorine-containing polymer in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. Solution polymerization, suspension polymerization, and emulsion polymerization are mentioned as such a polymerization method. In particular, solution polymerization is preferable.

In solution polymerization, in the presence of a polymerization initiator, after dissolving a monomer in the organic solvent and carrying out nitrogen substitution, the method of heat-stirring for 1 to 10 hours in 50-120 degreeC is employ | adopted, for example. As a polymerization initiator, for example, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxy pivalate And diisopropyl peroxydicarbonate. You may use a polymerization initiator in the range of 0.01-5 weight part with respect to 100 weight part of monomers.

As an organic solvent, it is inert to a monomer and melt | dissolves these, For example, a pentane, hexane, heptane, an octane, isooctane, cyclohexane, benzene, toluene, xylene, a petroleum ether, a commercial petroleum solvent (EXXSOL D40 by Exxon Mobil Corporation, ISOPER E, etc.), tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, t-butyl acetate, isopropanol, propylene glycol methyl ether acetate, p -Chlorobenzotrifluoride, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. Can be mentioned. You may use the organic solvent in 50-1000 weight part with respect to 100 weight part of total monomers.

After the polymerization reaction, an aqueous solution of the polymer can be obtained by adding water to the reaction mixture and removing the organic solvent (by distillation or the like).

In the present invention, the coating agent (for example, a water / oil repellent agent or an antifouling agent) comprises (1) a fluorine-containing polymer and (2) an aqueous liquid medium, that is, water or a mixture of water and a water-soluble organic solvent. Examples of water soluble organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol; Ketones such as acetone and the like. The amount of the water-soluble organic solvent may be 50% by weight or less, for example, 1 to 30% by weight based on the mixture (total of water and water-soluble organic solvent).

The coating agent is in the form of a solution (aqueous solution) of the fluorine-containing polymer.

In the coating agent, the amount of the fluorine-containing polymer is not particularly limited, and may be appropriately selected within a range in which it can be dissolved uniformly. For example, it may be 0.1 to 50% by weight, for example 0.2 to 20% by weight, in particular 0.5 to 10% by weight, based on the coating agent.

The coating agent of this invention may contain (3) additive in addition to (1) fluoropolymer and (2) aqueous liquid medium.

Examples of the additive (3) are silicon-containing compounds and the like.

It is preferable that a silicon-containing compound is a compound which has at least 1 siloxane bond. A silicon containing compound is a compound except the monomer which has a silane group generally.

The silicon-containing compound is, for example, an alkyl silicate, a silicate, or the like.

Examples of the alkyl silicate may be a compound represented by the following general formula (IV).

<Formula IV>

In formula, R <^1n> represents a C1-C18 alkyl group, and when nn is two or more, it may be same or different, and R <^2n> represents a hydrogen atom or a C1-C5 alkyl group, and nn is two or more May be the same as or different from each other, and nn represents an integer of 1 to 20.

With respect to R ¹ⁿ , the alkyl group having 1 to 18 carbon atoms (that is, saturated aliphatic hydrocarbon group) is not particularly limited, and examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and jade. Tyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. are mentioned, These may be linear or branched form It may be.

With respect to said R <^2n> , it does not specifically limit as a C1-C5 alkyl group, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. are mentioned, These may be linear or branched form.

Nn is an integer of 1 to 20, for example 1 to 10.

More specifically, as the alkyl silicate, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyl Limethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, Pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxy Silane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxy Silane, Tridecyl triethoxy silane, tetradecyl triethoxy silane, pentadecyl triethoxy silane, hexadecyl triethoxy silane, heptadecyl triethoxy silane, octadecyl triethoxy silane, etc. are mentioned, Among these, methyl Trimethoxysilane, methyltriethoxysilane, hexyltriethoxysilane, and octyltriethoxysilane are preferable.

Moreover, the dimer of a silicon-containing compound, etc. can also be used as a silicon-containing compound, As this, nn is 2 or 3 in the said general formula (IV), etc. are mentioned. In addition, nn may be an integer up to 20.

Siliconates (particularly alkylsiliconates) are, for example, formulas

R ¹ _a Si (OR ² ) _b (OM) _c [where a is an integer greater than or equal to 0 (preferably 1), b is an integer greater than or equal to 0 (preferably 2), and c is an integer greater than or equal to 1 (preferably 1), satisfying a + b + c = 4, R ¹ may be the same or different, represents a hydrocarbon group having 1 to 18 carbon atoms, R ² may be the same or different, and is a hydrogen atom or carbon number; A hydrocarbon group of 1 to 18, M may be the same or different, and represents an alkali metal.

The hydrocarbon group is, for example, an aliphatic hydrocarbon group (for example, an alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group.

As R ¹ , for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 2,2,4-trimethylpentyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, cyclo Pentyl group, cyclohexyl group, cycloheptyl group, methylcyclohexyl group, phenyl group, naphthyl group, anthryl group, phenanthryl group, tolyl group, xylyl group, ethylphenyl group, benzyl group, phenylethyl group and the like. Among these, a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is especially preferable.

Examples of R ² include the same groups as R ^{1 in} addition to the hydrogen atom. Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is especially preferable.

Li, Na, K, etc. are mentioned as M, Especially Na is preferable.

Specific examples of the alkylsiliconate are sodium methylsiliconate [CH ₃ Si (OH) ₂ (ONa)] and potassium ethyl silicononate [C ₂ H ₅ Si (OH) ₂ (OK)].

The amount of the additive (3) may be 0 to 200 parts by weight, for example 0 to 50 parts by weight, for example 0.1 to 50 parts by weight, based on 100 parts by weight of the fluorine-containing polymer (1).

In addition, the coating agent, in addition to the components (1) to (3), if necessary, other water repellents, other oil repellents, fluorescent agents, drying rate modifiers, crosslinking agents, film preparation aids, compatibilizers, surfactants, cryoprotectants, viscosity You may contain a regulator, a ultraviolet absorber, antioxidant, a pH adjuster, an antifoamer, a slipperiness regulator, an antistatic agent, a hydrophilic agent, an antibacterial agent, a preservative, an insect repellent, a fragrance | flavor, a flame retardant, a color adjuster, etc.

In this invention, a coating agent is apply | coated to a base material and a moisture proof property is provided to a base material.

Examples of the substrate include electronic components and electrical components. In the present specification, when simply referred to as "electronic component", an electrical component is also meant in addition to the electronic component.

A base material is an electronic component and an electrical component arrange | positioned in the place exposed to moisture, outdoor and indoor, and are an electronic component and an electrical component in which the circuit was installed and the various elements were attached. Examples of the substrate are a circuit board, a bearing of a hard disk, and the like. Electronic components and electrical components are, for example, in articles such as telephones, signals, air conditioners, outdoor units, switchboards, columnar capacitors, mobile phones, mobile relay antennas, automotive electronic devices, ship electronic devices, vending machines, mobile personal computers, and the like. Used.

As an electronic component, although various printed wiring boards (electronic circuit boards), a hybrid IC, etc. can be illustrated, it is not limited to these.

As the substrate material of such electronic components, epoxy resins, phenol resins, BT resins, polyimides, glass fabrics (fibers), aluminum, and the like are used, and metals such as copper, silver, gold and platinum are used as circuit materials. Solder is also scattered on the substrate. The coating composition of the present invention does not alter these materials.

In addition, as an electrical component, a switchboard etc. can be illustrated besides the various electrical apparatus which embed | bushed said electronic component. Specifically, the outdoor unit of the air conditioner, mobile phone, car navigation system, solar panel, lighting, signal signal, mobile relay antenna, automotive electronic equipment, vending machine, mobile personal computer, unmanned antenna station, radio, marine equipment, clock, etc. It can be illustrated.

The coating agent is applied by a brush coating method, a dipping method, a spray method, a roll coating method, a potting method, a casting method, or the like, and is left in the surrounding environment to volatilize the aqueous liquid medium to form a coating film.

In the present invention, the coating film may be a film produced from the coating composition, for example, a casting film. This film obtains a moisture proof effect by wrapping electronic and electrical components.

The substrate is treated (especially applied) with the coating agent. The amount of coating agent is 0.05 to 50 g / m ² , for example 0.1 to 25 g / m ² , preferably 0.5 to 5.0 g / m ² as the fluorine-containing polymer in the coating. Application | coating may be performed once, but you may divide into multiple times.

"Treatment" means applying a processing agent to a base material by immersion, spraying, application | coating, etc. By treatment, the fluorine-containing polymer which is an active ingredient of the treatment agent adheres to the surface of the substrate (and / or penetrates into the interior of the substrate).

<Examples>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this is only the specific example of this invention, and this invention is not limited to it. In the following,% is% by weight unless otherwise specified.

The test method and the measurement method employ | adopted by this invention and the following Example are as follows.

(1) water- and oil-repellent

The water / oil repellency of the copper foil of the test piece was evaluated using a contact angle meter (CONTACT-ANGLE METER CA-DT manufactured by Kyowa Kaimen Chemical Co., Ltd.).

(2) resistance value

The surface resistance of the test piece was measured by the electrical resistance measuring instrument (ULTRA HIGH RESISTANCE METER R8340A by Advan Test Co., Ltd.).

(3) water resistance

The test piece was immersed in 25 degreeC deionized water for 24 hours. The surface resistance of the test piece after immersion was measured by the electrical resistance measuring instrument.

(4) dryness

The coating agent was apply | coated to the glass fiber reinforced epoxy resin board which installed the comb-shaped electrode substrate by the brush coating method, and the surface resistance of the test piece was measured with the electrical resistance measuring instrument, drying at room temperature.

(5) high temperature and high humidity

The test piece is placed in a high temperature and high humidity bath maintained at 85 RH% at 85 ° C. for 48 hours, and the voltage at 16 V is continuously applied. When measuring resistance value, the voltage of 100V was applied and the time-dependent change of the resistance value under high temperature, high humidity was investigated.

Production Example 1 (Preparation of Aqueous Polymer Solution of "Rf (C6) -DM")

CF ₃ CF _2- (CF ₂ CF ₂ ) ₂ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ [Rf (C6) methacrylate] 73.30 g, dimethylaminoethyl methacrylate (DM) 26.70 g, isopropanol After stirring and dissolving 150.00 g of (IPA) in a four-necked flask, the mixture was kept at 60 ° C with nitrogen substitution, 2 g of t-butylperoxy pivalate was added and reacted at 60 ° C for 6 hours to obtain a polymer solution. The completion | finish of a polymerization reaction confirmed the conversion rate of monomer more than 99% by gas chromatography. In addition, the polymer solution with stirring at 60 ℃, was added dropwise CH ₃ COOH (acetic acid) and 10.20g of a mixture of ion-exchanged water 300g. Thereafter, IPA was removed under reduced pressure, and the solid content of this solution was obtained from the evaporation residue after heating at 130 ° C. for 1 hour, and diluted with ion-exchanged water so that the solid content was 25% by mass to obtain a transparent and stable aqueous polymer solution.

Preparation Example 2 [Rf (C4) Cl-DM] and Preparation Example 3 [Rf (C2) -DM]

Rf (C6) methacrylate and DM in Preparation Example 1 were each substituted with CF ₃ CF ₂ CF ₂ CF ₂ -CH ₂ CH ₂ OCOC (Cl) = CH ₂ [Rf (C ₄ ) chloroacrylate], DM. Except having substituted by 37.00g, what was manufactured by the exact same method was used as the preparation example 2. Also, Preparation Example 3 was prepared in exactly the same manner except as substituted with 59.62 g of CF ₃ CF ₂ -CH ₂ OCOC (CH ₃ ) = CH ₂ [Rf (C2) methacrylate] and DM 40.38 g. It was.

Example 1

Coating agent (manufacturing example 1 thru | or) with the glass-fiber reinforced epoxy resin board (material: CEM3, plate thickness: 1.6 mm, copper foil thickness: 18 micrometers, pattern width: 0.75 mm or 0.3 mm) provided with the comb-shaped electrode substrate by the brush coating method. 3 polymer aqueous solution) was apply | coated and dried, and the test piece of the film thickness of 2.7 micrometers of coating was created. The water repellent oil repellency, the resistance value, and the high temperature and high humidity resistance were measured about this test piece (the test piece which apply | coated the polymer aqueous solution of Example 1). The results are shown in Tables 1-4.

Example 2

The same procedure as in Example 1 was repeated except that the film thickness of the coating was changed to 0.8 mu m. The results are shown in Tables 1-4.

Comparative Examples 1 and 2

The same procedure as in Example 1 was repeated except that the type of coating agent and the film thickness of the coating were changed. As a comparative example, a urethane-based dispersion ("Takerak W-6020" made by Mitsui Chemicals Polyurethane Co., Ltd.) and an acrylic-based dispersion ("Viniblan Vinniblan T0-453N" made by Nisshin Chemical Industries, Ltd.) are used. It was. The results are shown in Tables 1-4.

The coating agent of this invention can be used for the moisture proof coating of an electronic component and an electrical component. Examples of electronic components and electrical components are circuit boards, hard disk bearings, and the like. Electronic components and electrical components are, for example, telephones, signaling devices, air conditioners, outdoor units, switchboards, columnar capacitors, mobile phones, mobile relay antennas, automotive electronic devices, ship electronic devices, vending machines, mobile personal computers, and the like.

Claims (13)

Coating agent for electronic components containing a fluorine-containing compound (1) and an aqueous liquid medium (2). The coating agent for electronic parts according to claim 1, wherein the fluorine compound (1) is a polymer comprising a repeating unit derived from a fluorine-containing acrylate monomer. The fluorine-containing compound (1) according to claim 2,
(A) repeating units derived from fluorine-containing acrylate monomers, and
(B) repeating units derived from amino group-containing monomers
Coating agent for electronic components which is a polymer comprising a. The fluorine-containing acrylate monomer (A) according to any one of claims 1 to 3,
At least one fluorine-containing group (hereinafter referred to as a "fluorine-containing group") selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group, and

[Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are hydrogen atoms) , A fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, and the like. Coating agent for electronic components which is a monomer which has an unsaturated group. The coating agent for an electronic component according to any one of claims 1 to 3, wherein the fluorine-containing acrylate monomer (A) is represented by the following general formula (I).
<Formula I>

Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are hydrogen atoms, Fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic aliphatic group, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or -CH ₂ CH (OY ¹ ) CH ₂ -group (wherein Y ¹ is a hydrogen atom or an acetyl group),
Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 2 to 21 carbon atoms, or a repeating unit -C ₃ F ₆ O-, -C ₂ F ₄ O-, and -CF ₂ O- It is a fluoroether group whose total number of at least 1 sort (s) of repeating units chosen from the group which consists of 1-200 is 1-200. The coating agent for electronic components according to claim 5, wherein Rf of the fluorine-containing acrylate monomer (A) is a fluoroalkyl group having 2 to 6 carbon atoms or a fluoroalkenyl group having 3 to 6 carbon atoms. The coating agent for electronic components according to any one of claims 1 to 3, wherein the amino group-containing monomer (B) is represented by the following general formula (II).
<Formula II>

Wherein R ¹¹ , R ¹² , R ²¹ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y ¹¹ is an oxygen atom or NH, and Z is a branched or straight chain having 1 to 10 carbon atoms It is an alkylene group, and R <^11> and R <^12> may combine with each other, and may form the ring with the adjacent nitrogen atom. The coating agent for an electronic component according to any one of claims 1 to 3, wherein the aqueous liquid medium (2) is (i) water or (ii) a mixture of water and a water-soluble organic solvent. The coating agent for an electronic component according to any one of claims 1 to 3, comprising a fluorine-containing compound (1), an aqueous liquid medium (2), and an additive (3). The coating agent for electronic components according to claim 9, which contains a fluorescent agent or a dye as the additive (3). The manufacturing method of the processing electronic component containing apply | coating an electronic component or an electrical component with the coating agent for electronic components in any one of Claims 1-3. 12. The method of claim 11, comprising removing the aqueous liquid medium after applying the coating for the electronic component to the electronic component or the electrical component. The process electronic component manufactured by the manufacturing method of the process electronic component of Claim 11.